Sciencemadness Discussion Board - Hypergolic Reactions and Energetics

Hypergolic Reactions and Energetics

Formatik - 5-7-2008 at 04:01

How about substances that explode on mixing? E.g.:

A mixture of about 90% H2O2 and conc. H2SO4 in a one-to-one volume ratio, in a drop amount will react extremely violently (near explosion) with a drop acetone added producing ignition and shooting the acid. Though drop amounts of either ethanol or ether with the same mixture do not show a reaction.

Ether is said to potentially interact explosively with anhydrous HNO3 (Bretherick’s), conc. HNO3 and ether in presence of conc. H2SO4 are said to explode violently. In the drop amounts, I was able to establish a violent interaction, but no ignition both with brown fuming HNO3 (with a d= 1.52) and this mixed with conc. H2SO4 (1:1 volume).

DMSO is said to react very violently and even explosively with acyl and nonmetal halides (e.g. acetyl chloride, cyanuric chloride, PCl3, S2Cl2, SOCl2, etc), notably oxalyl chloride.

MeOH can oxidize explosively from HNO3 if nitrogen oxides are present. In drop amounts, reddish fuming HNO3 (d = 1.52) added to MeOH showed no visible interaction.

Title Changed, Chemoleo

[Edited on 6-12-2008 by chemoleo]

grndpndr - 10-7-2008 at 01:17

WW2 german rocket technology used very dangerous hypergolic chemcals as fuels for rocket planes
C-stoff and T-Stoff were the german names of the chems. T-Stoff 90%, Hyd Per/ C-Stoff, Hydrazine Hydrate,methanol,water.

later another rocket engne operating on similar principles used a different mixture 98+ NA oxidizer/Kerosene fuel

[Edited on 10-7-2008 by grndpndr]

[Edited on 10-7-2008 by grndpndr]

Formatik - 10-7-2008 at 16:32

T-Stoff was the name for highly concd. H2O2. I have a book on German rockets it’s called Flugkörper und Lenkraketen (1987), they say the optimal concentration of the H2O2 was between 80 to 85%, and the rest water, higher concentrations did give better performance, but were difficult to control, in addition that higher conc. peroxide is an explosion risk and will freeze easily by a light frost. C-Stoff is 57% N2H4 hydrate, 30% methanol and 13% water with the addition of a small amount of potassium cuprocyanide (0.6 g/L). This combination was also used for propulsion of Messerschmitt Me 163 B, but not without some horrible failures.

The reason for the catalyst, because highly concd. H2O2 will not react quickly enough with hydrazine hydrate, unless catalysts are present. But it is said 1,1-dimethylhydrazine reacts more easily. N2H4 itself also tends to ignite from some catalysts and fine material. N2H4 has also found some use as a monopropellant as it burns after being ignited even without an atmosphere of oxygen.

I've read gasoline and HNO3 are hypergolic. A drop of the strong fuming HNO3 added to two drops gasoline only showed an evolution of nitrogen oxides. Kerosene in the same instance just turns dark with the acid, and no gas evolution. More exciting would be observing the reactions of N2H4 with some oxidizers, but it is a hell to make.

[Edited on 10-7-2008 by Schockwave]

Axt - 10-7-2008 at 17:28

N2O4 detonates on mixing with N2H4. and rapidly ignites glyoxime.

To state the obvious Mn2O7 explodes with a bang on contact with xylene.

Sodium nitromethanate (aka sodium methylnitronate) is said to ignite on contact with water, however it won't for me. Though I know it ignites on contact with Cl2.

Formatik - 10-7-2008 at 18:50

Mn2O7 explodes on contact with almost any simple organic material as it is itself explosive (shock sensitivity also like Hg-fulminate) and a powerful oxidizer, but even with finely divided materials like Ag2O or MnO2 bring a reaction. Itself it is a weak explosive having a VOD of 400 m/sec. according to Gmelin Mn [C1] p. 366, I could imagine on contact with a fuel it becomes quite powerful.

Plain hypergolic reactions themselves are easier to come by than the stronger reactions. Sodium dichloro-s-triazinetrione in a small powdered pile ignites a drop of DMSO evolving gas and a garlic odor. KMnO4 will also ignite DMSO in those amounts if it is a dust. KMnO4 of 20% in RFNA is said to make the acid immediately hypergolic with the basic alcohols (MeOH, EtOH, etc), but it didn't work in drop amounts by me. KMnO4 ignites also with an array of compounds, notably polyalcohols glycerol, glycol, some brake fluids, etc. though usually with some delay, and it is said to explode with N2H4.

[Edited on 10-7-2008 by Schockwave]

vulture - 11-7-2008 at 16:09

Solid KClO3 and conc H2SO4 should explode upon mixing. I wonder what happens with conc HNO3...

ShadowWarrior4444 - 11-7-2008 at 19:07

Quote:

Originally posted by vulture
Solid KClO3 and conc H2SO4 should explode upon mixing. I wonder what happens with conc HNO3...

I recall that pyrotechnic mixtures using both a chlorate and a nitrate are generally not used because they are prone to spontaneous unintended detonation. I suspect that would be the case here, probably with the evolution of some particularly enjoyable NO and NOCL varieties.

Formatik - 12-7-2008 at 17:57

Quote:

Originally posted by vulture
Solid KClO3 and conc H2SO4 should explode upon mixing.

H2SO4 and KClO3 forms HClO3, which is of course very unstable. The highest concentration of HClO3 which is said to be obtainable and handable is 40%. Higher concentrations decompose to HClO4, ClO2, and Cl2.

A few drops of conc. H2SO4 added to a small pile of KClO3 turned it red and frothed giving off some gases (likley ClO2, Cl2). Dipping in a tissue into this causes snaps and crackles. Adding a few drops of conc. H2SO4 to a larger quantity mixture of KClO3 and sugar or starch, etc. is another well known hypergolic ignition reaction, although it can be a bit more violent than a simple ignition. There are a couple videos on YouTube.

A small KClO3 pile, enough to absorb about 1 drop ethanol ignited and burned violently after 2 drops H2SO4. In the same case but using 2 drops methanol, also a more violent ignition and reaction. Slightly oversaturating a pile of KClO3 with 1 drop glycerin then 2 drops H2SO4 causes frothing and gas evolution, but when the mixture was stirred with a rod, it shot out some flames.One drop acetone absorbed onto a small KClO3 pile quickly having 2 drops H2SO4 added turned red and gave off some gases. A small pile of KClO3 having a few drops DMSO (slight oversaturation) caused a violent ignition and strong burning reaction when the H2SO4 was added. A few drops of ether absorbed onto KClO3 caused immediate ignition as soon as the H2SO4 contacted the mixture. In some of the mixtures, the acid also shoots out. I thought the reactions with methanol could form the dangerous methyl perchlorate which is said to be more brisant than CH3ONO2.

Quote:

I wonder what happens with conc HNO3...

I doubted these would react, and I tried it with a small pile of KClO3 (around 0.1 g) with several drops of reddish fuming HNO3 (d = 1.52), it didn't show any visible reaction or color change as the acid saturated the chlorate, but a tissue dipped into this mixture caused sizzling, charring and sparking evolving a significant volume of gas. Adding several drops methanol to a small pile of KClO3, on the addition of 1 drop of the HNO3 gave an audible pop and set fire to the rest of the methanol.

Quote:

Originally posted by ShadowWarrior4444 I recall that pyrotechnic mixtures using both a chlorate and a nitrate are generally not used because they are prone to spontaneous unintended detonation. I suspect that would be the case here, probably with the evolution of some particularly enjoyable NO and NOCL varieties.

Are you are thinking of nitrate and aluminum powder which can ignite spontaneously (especially when wet)? Maybe also chlorates mentioned here mixed with sulfide or sulfur (especially sulfur flower), which can ignite spontaneously. I think you might actually mean ammonium nitrate together with a chlorate salt, that is a definite spontaneous explosion risk.

[Edited on 13-7-2008 by Schockwave]

Formatik - 16-7-2008 at 16:54

This one is more of an ignition. Even though the following will react immediatley and strongly under large gas evolution and sizzling alone, the permanganate was needed for ignition. Adding a drop of turpentine to a drop of the strong fuming HNO3 containing some KMnO4 powder caused a flame to flash out. Reportedly, it is said other catalysts work: FeCl3, CuCl2, oleum, NH4VO3, for turpentine to cause ignition with the fuming acid.

[Edited on 16-7-2008 by Schockwave]

Zinc - 17-7-2008 at 05:53

I have heard that turpentine can ignite when exposed to chlorine, is that true?

Formatik - 17-7-2008 at 11:51

Quote:

Originally posted by Zinc
I have heard that turpentine can ignite when exposed to chlorine, is that true?

Negative, by my experience. I put a drop of turpentine onto a plastic carrier and lowered it into a graduated cylinder containing a chlorine generator of conc. HCl and KMnO4, and the drop didn't ignite. I also generated some Cl2 in a bottle and poured it out into a dish containing a few drops turpentine, and again no reaction. Here it's said to be able to ignite it, maybe then in a warm reaction condition, or larger amounts and allowing it to sit for a bit.

But I've also tried different chlorinating compounds. No reaction of turpentine with powdered pile of sodium dichloro-s-triazinetrione. A chlorinator containing: 1-bromo-3-chloro-5,5-dimethylhydantoin (60%), 1,3-dichloro-5,5-dimethylhydantoin (27.4%), 1,3-dichloro-5-ethyl-5-methylhydantoin (10.6%) and the rest inert. A powdered pile of this with a few drops turpentine absorbed after a few short seconds made a large amount of gas, but did not ignite it. In the similar instance, this same chlorinator reacts instantly with DMSO producing gas but no ignition.

A compound that is said to ignite turpentine is chromyl chloride, CrO2Cl2. This is easy to make, but it is nasty stuff. It is also said to ignite acetone, ethanol, ether, H2S, NH3, sulfur, urea, and explode moist phosphorus.

[Edited on 18-7-2008 by Schockwave]

PHILOU Zrealone - 18-7-2008 at 01:49

HNO3 conc + KClO3 in significant amount will burst into flame

H2O2 (50%) + red phosphorus (10 second delay)...evolution of acidic white smokes

KMnO4 + glycerine or glycol (from a few second to a few minutes delay) hanging on the cristal size, the size of the batch and the external temperature..glycol will react faster than glycerine because it is less viscous. In winter can take serval minutes while in summer 1/3 of a minute

H2O2 (50%) + Aceton + HCl (35%) at ambiant T without cooling boils and then makes a big cloud of tear gas... for sure explosive with H2SO4 conc as explained above by Shockwave ...

Na, K, Rb, Cs with water...the two last are super explosive.

...

[Edited on 18-7-2008 by PHILOU Zrealone]

Formatik - 18-7-2008 at 02:06

Quote:

Originally posted by PHILOU Zrealone
HNO3 conc + KClO3 in significant amount will burst into flame

H2O2 (50%) + red phosphorus (10 second delay)...evolution of acidic white smokes

KMnO4 + glycerine or glycol (from a few second to a few minutes delay) hanging on the cristal size, the size of the batch and the external temperature..glycol will react faster than glycerine because it is less viscous. In winter can take serval minutes while in summer 1/3 of a minute

H2O2 (50%) + Aceton + HCl (35%) at ambiant T without cooling boils and then makes a big cloud of tear gas... for sure with H2SO4 conc as explained aboveby Shockwave explosive...

Hi Louis. The glycerin reaction is classical. I think KMnO4 might also ignite some glycol ethers. As a control to the 90%, in the same instance with 35% H2O2 and H2SO4 there was no reaction with acetone, not even gas evolution. But that is also at small amounts.

AngelEyes - 18-7-2008 at 06:17

"instance with 35% H2O2 and H2SO4 there was no reaction with acetone"

- forgive me, but doesn't that make a well known dimeric peroxide?

Formatik - 18-7-2008 at 11:36

I don't know and doubt if they will survive that strong of an acidity. Wether the trimer or dimer forms is dependent on reaction temperature, with cooler temperatures favoring the trimer. But the point is there was no ignition, gas evolution, etc. as with the almost explosive violence that highly concentrated peroxide reacts with at the drop level.

ShadowWarrior4444 - 18-7-2008 at 15:26

Acetone peroxide is created using a small amount of acid catalyst. Excess acid can produce mesityl oxide or diacetone alcohol.

As for having no reaction between acetone, H2O2 and H2SO4, that is strictly impossible unless the H2SO4 was highly dilute. H2SO4+35% H2O2 will make something called "Pirahna Soultion" that is not only capable of massacring anything organic, but also oxidizing carbon to carbon dioxide.

That said, it shouldn’t necessarily 'explode,' but there will be a reaction.

Ancillary: KMnO4 has been known to ignite Ethylene Glycol slightly slower than it does glycerol.

[Edited on 7-18-2008 by ShadowWarrior4444]

chloric1 - 18-7-2008 at 16:09

No mention of calcium hypochlorite? With glycerine, in small quantities, no flame but rapid gas evolution after delay. I suspect 10's of gram quantities would inlfame but I have not tried this because of phosgene generation. I am fairly sure phosgene is generated because the smoke is pungent in a sweetish way totally unlike HCl and Cl2. Hypochlorite and other solid chlorinators seem to inflame with brake fluid which is made up various polyglycols. I wonder about hydochlorite and the alcohols when not confined. Obvously they give off a loud report when in closed containers but you never see a flash.

Formatik - 25-7-2008 at 05:59

Quote:

Originally posted by ShadowWarrior4444
Acetone peroxide is created using a small amount of acid catalyst. Excess acid can produce mesityl oxide or diacetone alcohol.

As for having no reaction between acetone, H2O2 and H2SO4, that is strictly impossible unless the H2SO4 was highly dilute. H2SO4+35% H2O2 will make something called "Pirahna Soultion" that is not only capable of massacring anything organic, but also oxidizing carbon to carbon dioxide.

That said, it shouldn’t necessarily 'explode,' but there will be a reaction.

To be clear, in such small amounts these don't react visibly. But in larger amounts, it's a different story.

Quote:

Ancillary: KMnO4 has been known to ignite Ethylene Glycol slightly slower than it does glycerol.

Both glycol and brake fluid (polyalkylene glycol ethers) react a bit quicker than glycerol, brake fluid quicker than glycol. Powerlabs also tested propylene glycol and found this took even longer than glycerin. DMSO reacts instantly with KMnO4, but the only way I’ve gotten an ignition with this, is if the KMnO4 was pulverized to a fine dust. The brake fluid has quite a short delay and out of all of these seems to produce the most powerful burning flame.

Quote:

Originally posted by chloric1
No mention of calcium hypochlorite? With glycerine, in small quantities, no flame but rapid gas evolution after delay. I suspect 10's of gram quantities would inlfame but I have not tried this because of phosgene generation. I am fairly sure phosgene is generated because the smoke is pungent in a sweetish way totally unlike HCl and Cl2. Hypochlorite and other solid chlorinators seem to inflame with brake fluid which is made up various polyglycols. I wonder about hydochlorite and the alcohols when not confined. Obvously they give off a loud report when in closed containers but you never see a flash.

Here is what Brethericks says about Ca(OCl)2: “Contact of the solid hypochlorite with glycerol, diethylene glycol monomethyl ether or phenol causes ignition within a few min, accompanied by irritant smoke, especially with phenol (formation of chlorophenols). Ethanol may cause an explosion, as may methanol, undoubtedly owing to formation of the alkyl hypochlorites. Reaction with polyethylene glycol hydraulic fluid may produce ignition, with a fireball.”

I’ve tried it with brake fluid onto small powdered piles (around the 1 to 2g range) of aged Ca(OCl)2 (65%, rest is inert), trichloro-s-triazintrione (TCCA), sodium dichloro-s-triazinetrione, and the halogenator above comprising halogenated hydantoins. None of them showed a visible reaction after sitting several minutes, besides later some of them gave a little gas evolution or color changes. I also got no visible reaction of few drops glycerin absorbed onto small piles of sodium dichloro-s-triazinetrione, trichloro-s-triazinetrione, and the several years old Ca(OCl)2 (maybe too old, but still has Cl2 smell).

A simple ignition that I would say is worth more and fail-proof than alcohol attempts is with sodium dichloro-s-triazinetrione. Dripping DMSO onto a small powdered pile of this will instantly cause a flame and a sustaining fire to form. This even works with DMSO which has 10% H2O in it. The gases from this reaction are awful and should also not be inhaled.

Chromyl chloride: this is a dark red liquid which strongly fumes, and its fumes will quickly color materials (plastics, stone, etc) yellow and red like its fumes, to even black, and it must not be handled without something like a gas mask, chemical resistant gloves and good ventilation. I did several experiments with this one, at first the reactions were done on a flat surface, then in small dishes.

On the flat plane: 3 drops turpentine had dropwise 3 drops CrO2Cl2 added, eventually after about the third drop a flame quickly flashed out but no fire. Few drops chloride with a few drops acetone gave no visible interaction. 1 drop CrO2Cl2 no visible interaction with 1 drop DMSO. 4 drops dropwise CrO2Cl2 onto 2 drops glycerol gave no visible reaction. 1 drop CrO2Cl2 onto 2 drops brake fluid (glycol ethers) fizzed slightly, no significant gas release. 1 drop CrO2Cl2 added to few drops ether caused sizzling, some gas but no ignition. Few drops chloride dropwise onto a pile of sulfur flowers caused sizzling and gas evolution, but no ignition. A couple drops chloride onto a tissue didn’t sizzle or ignite. By no visible reaction I mean: ignition, sizzling, gas evolution.

In separate small shallow dishes: 2 drops CrO2Cl2 dripped into 5 drops ethanol instantly caused a flame to flash out strongly and ignite the ethanol. 1 drop CrO2Cl2 ignited 5 drops methanol on contact. Several drops ether in the dish then dropwise CrO2Cl2 several drops, this only sizzled and gas release, and again no ignition. 6 drops turpentine caught on fire from 1 drop chloride, but the alcohols seemed more vigorous in ignition. 8 drops acetone from 1 drop CrO2Cl2 added, it gave sizzling reaction and red gases, no ignition; the same is with 8 drops M.E.K. and 3 drops chloride added dropwise, but the reaction seems weaker.

I also tried some reactions with liquid N2O3 (indigo blue liquid), and it is not a very exciting substance (no ignition with ethanol, ether, toluene, or DMSO in the drop amounts on a flat surface). Chromyl chloride was a more interesting oxidizer.

Concerning alkali metal reactions with water. The reaction of sodium seems more or less predictable if it will ignite and burn when put onto water in small pieces. When I was a teen I was trying to form Na2O2 by heating Na metal in air, this amount of Na was about as much as that seen in this video reacting with water. It did form a solid layer and stuck to the glass, but for some reason I threw it into a paint bucket containing water and it caused a loud explosion and a massive volume of gas. Na2O2 itself will react violently with water and powdered metals. I can't verify it again, but I think the Na reacted with the Na2O2 to produce a more violent reaction.

Request to moderators: I think this thread title would be appropriately "Hypergolic reactions", and in my beginning post it should read compounds which "substances that ignite or explode by mixing". Since this thread also largely covers ignition reactions.

Formatik - 26-7-2008 at 19:09

Quote:

I think the Na reacted with the Na2O2 to produce a more violent reaction.

Either this, or the sodium which got stuck to the glass got dragged under water causing the sodium to react all at once as instead of dancing on top of it and fizzing around igniting at will like it usually does in those amounts.

Formatik - 21-8-2008 at 15:22

Another simple oxidant worth investigating is bromine trifluoride (BrF3) made by just combining F2 with Br2. Much more reactive, toxic and difficult to handle than CrO2Cl2, being a strongly poisonous fuming liquid which is said to react explosively with water, and possibly be able to explode on contact rubber, plastics and organics. It is said to explode on contact with ether or acetone. Violent reaction with many compounds and materials like cork, wax, etc. A milder one but still strong oxidant to experiment with would be IF5, this can be made from I2 and F2 (e.g. US4108966). For an amateur it could be possible to distill I2 and AgF in a copper vessel and collect the IF5 in Cu (forms passive fluoride layer) or PTFE container.

JohnWW - 22-8-2008 at 07:09

IF7 is preferentially formed by direct reaction of I2 with F2, however. I understand that IF5 tends to disproportionate to IF7 and F2.

Formatik - 3-12-2008 at 23:13

I've tried other oxohalogenates also. KBrO3: 0.4 g KBrO3 and 5 drops EtOH (95%), 1 drop conc H2SO4 just sizzles and gives white and red fumes; the same if more H2SO4 is added dropwise. Then: 0.2g KBrO3, 2 drops 90% DMSO, and 1 drop H2SO4 decomposed under fizzing and large gas evolution also with no ignition. 0.3 g KBrO3 mixed with 0.1 g cane sugar, after 1 drop H2SO4 this mixture immediatley ignited and goes nearly as a flash powder with a bright white-blue light, large gas cloud and creating noise as it burns. For comparison, 0.3 g KClO3 and 0.1 g cane sugar mixture ignited from 1 drop H2SO4, and burns vigorously with a purplish flame, it typically burns slower than the -BrO3. The videos of these two reactions are below.

KIO3: 0.3 g KIO3 and 0.1 g cane sugar mixed, 1 drop H2SO4 showed no reaction, 3 drops more and still no reaction. 0.2 g KIO3 and 2 drops 95% EtOH, then 1 drop H2SO4; nothing. After 2 drops acid, the same even after mixing them around and still no reaction. I didn't expect much from the KIO3, it's a flimsy oxidizer.

http://rapidshare.com/files/170080763/KBrO3-sugar.MOV.html
http://rapidshare.com/files/170081423/KClO3-sugar.MOV.html

chief - 4-12-2008 at 06:37

@Formatik: About the piranha-solution with carbon: Does it also oxidize graphite ? And at what rate ? Is there a possibility, that CO can be generated ?
Does the carbon have to be finely divided, or will it attack larger pieces at a considerable rate ?

hissingnoise - 4-12-2008 at 10:40

Sucrose/NaClO3 (dried) mixtures ignite readily when conc. HCl is droppered on them.
The reaction surprised and mystified me as a child.

Formatik - 4-12-2008 at 18:39

Quote:

Originally posted by chief
@Formatik: About the piranha-solution with carbon: Does it also oxidize graphite ? And at what rate ? Is there a possibility, that CO can be generated ?
Does the carbon have to be finely divided, or will it attack larger pieces at a considerable rate ?

I haven't tried but think it should dissolve graphite. My only experience with Piranha and carbon is using it to dissolve carbonaceous residues from glass apparatuses, where I had to heat it to get it to work.

Quote:

Originally posted by hissingnoise
Sucrose/NaClO3 (dried) mixtures ignite readily when conc. HCl is droppered on them.
The reaction surprised and mystified me as a child.

I have tried using conc HCl (>31%) as an initiator and it didn't work. 0.3 g KBrO3 and 0.1 g sugar mix in a volcano-pile and it strongly effervesced (Cl2) from 1 drop conc HCl, more drops caused the same, it didn't ignite. Then I tested this with 0.3 g KClO3 and 0.1 cane sugar mixture in a volcano-pile, this turned green from 1 drop conc HCl, waiting a few seconds, more drops did the same and this also didn't ignite. HNO3 likley could pull off an ignition (if not conc, then fuming).

hissingnoise - 5-12-2008 at 05:41

Try it with the sodium salt; it contains a higher percentage of oxygen (than the K salt) which makes the reaction more vigorous, presumably.

Formatik - 5-12-2008 at 12:47

Quote:

Originally posted by hissingnoise
Try it with the sodium salt; it contains a higher percentage of oxygen (than the K salt) which makes the reaction more vigorous, presumably.

Will have to make some NaClO3 and LiClO3 some time. The latter has more O: 53% vs. 45%.

some more

Formatik - 20-12-2009 at 00:35

Below are some reaction experiments of the strong oxidant nitrosyl perchlorate, albeit impure. The compound nitrosyl perchlorate also has its own thread here. That's a good thread to look at about the compound. According to the lit. (e.g. Hofmann, Zedtwitz, Ber. 42, [1909] 2031) NOClO4 immediately forms methyl nitrite with methanol; ethanol, acetone, and ether inflame or explode after several seconds.

Also reacts extremely violently with the primary amines of the benzene group: aniline, o- and p-toluidine, mesidine, xylidine, apparently so due to intermediate diazonium perchlorates (extremely explosive compounds). Hofmann was able to prepare perchlorate esters from alcohols like glycol when the reaction wasn't too violent. Urea and many other compounds also ignite or react similar. In Lehrbuch der anorganischen Chemie (1919) by Karl A. Hofmann, he says the perchlorate is useful for a number of interesting demonstrations.

After prep. procedure from N2O3 and conc. HClO4, the NOClO4 couldn't be readily obtained anhydrous or acid-free and was mostly removed from the HClO4 by glass filtration. So in all attempts it was slightly moist with the HClO4, and the hydration water wasn't removed (NOClO4.H2O). Despite that some test were done to see what happens. Anhydrous material should yield more spectacular results. It can be washed with dry nitromethane to remove the acid, and then it can be dehydrated entierly by standing it with P2O5 in a vac. for a few days. Below was studied the reaction of only the moist oxidant with: diethylether, dimethylformamide, dimethylsulfoxide, ethanol, methanol, toluene, o-tolidine, acetone, methylethyl ketone, turpentine. Strongest reaction seen with the latter. The reactions likley become more violent if scaled up and with pure oxidant.

1.6g NOClO4 (so as said above, HClO4-moist) in a plastic cap had 5.1g anhydrous ether dumped in, when mixed there is a only very short delay in reaction and then it begins boiling, formaldehyde smell is given off among fumes. Eventually it stops boiling. No other reaction after around 2 minutes and beyond.

0.2g NOClO4 in plastic covered metal cap, then 0.5mL DMF added. After 4 minutes no significant interaction. So it was left standing for several minutes and eventually shaken, after which it began to give off a few bubbles and eventually quietly dissolved.

Small chunk of the NOClO4 maybe 0.2g on a flat surface with a few mL (maybe 0.4mL) 99% DMSO only frothed for some time.

In plastic cap, 0.4g of the NOClO4 had a few mL, maybe 0.5mL denatured alcohol dumped in, soon after the addition it started boiling, fruity acetaldehyde smell given off.

Then 0.1g NOClO4 in a plastic cap had several drops of methanol dumped in at once, and it rapidly starts boiling when the methanol is added.

Maybe like 0.2-0.5mL of toluene added to 0.3g NOClO4 in a plastic cap. As soon as the toluene was added the white solid turned reddish orange, and after standing long several minutes the solid turned a darker red-orange.

0.1g NOClO4 in a small cap, had a few drops o-tolidine added. As soon as a drop contacted the perchlorate, a vigorous reaction occured under the evolution of red-brown gases. No further reaction.

Small chunk amount of NOClO4 maybe 0.2g and a few small mL acetone on a flat surface was a very vigorous reaction, after a small delay a very large visible volume of dense white gases was evolved (it looked like it was about to ignite, but didn't). The smell was acetic to cyanic, but I didn't smell more to find out.

0.2g of the NOClO4 in a plastic cap had several drops MEK dumped in at once. Nothing happened until around 2 to 5 sec. after the MEK made contact, then it started boiling and a flame shot out violently, but the flame did not ignite the mixture. Visible gases given off. Acetone probably reacts similar in a cap (drenched).

0.1g NOClO4 in a plastic covered metal cap (used to screw closed glass bottles), had maybe about 0.2 to 0.5mL of turpentine dumped in. This changes color as some red appears. After around 8 to 10 seconds of addition, the mixture began bubbling and boiling a bit, and then after some more seconds the violence of bubbling increases until the mixture violently burst out into a flame and a sustaining fire formed (had to be extinguished by dumping water on it, blowing it out didn't work). Eucalyptus oil could yield similar results to turpentine since it also has pinenes and similar molecules.

Urbanski has some good information and section on subjects like this, e.g. organic amines with nitric acid hypergols and rocket fuels. I would highly recommend this for someone more interested in the subject.

franklyn - 20-12-2009 at 09:19

Related thread
http://www.sciencemadness.org/talk/viewthread.php?tid=6031

Calcium Phosphide ( Ca3P2 ) + H2O -> ( PH3 ) Phosphine
which pyrophorically burns with a bright cherry red flame.

http://www.youtube.com/watch?v=vgh76gPSg3M
Another mixture
http://dl.uncw.edu/digilib/chemistry/general/I-Al%20reaction...

Aluminum or Magnesium powder explodes in contact
with any Halocarbon solution of Iodine
Frozen slurry of Al or Mg with Halocarbon alone at temperatures
of liquid nitrogen -196 °C , explode upon thawing.

.

woelen - 21-12-2009 at 05:58

A few examples of self-ignition:

Demo 1
- Add a few drops of acetone to some solid NaClO2, such that the material is wetted completely
- Add a few drops of concentrated sulphuric acid and let is soak the material
- Add a small drop of water --> instant explosion with an orange flash of light

Demo 2
- Take a spatula full of powdered Na2O/NaOH mix and put this in a DRY testtube
- Add a few drops of nitromethane --> As soon as the liquid touches the solid a 10 cm long orange flame erupts out of the test tube!

Demo 3
- Take some solid Ca(OCl)2 swimming pool chlorine
- Take some powdered red phosphorus and carefully coarsely mix with a glass rod
- Just wait --> Usually within one minute the mixture ignites with a heavily smoking flame and popping/crackling noises

Demo 4
- Mix 100 mg or so of AgNO3 with an equal amount of magnesium metal (assure that both reagents are perfectly dry)
- Touch the mix with a long wet stick --> A very bright white flash occurs and droplets of molten silver are sprayed around

When doing these demos, please be careful and only use SMALL quantities and always be prepared to cope with (too) early ignition of the mixes. All 4 of these experiments, however, are nice and spectacular demos which can be carried out safely when done carefully.

I tried the NaClO3/conc. HNO3 suggestion further up in the thread, but it did not work for me. No reaction at all, the NaClO3 did not dissolve and the colorless crystals of NaClO3 became covered with a thin white crust. Apparenty some NaClO3 dissolves, giving a precipitate of NaNO3 which covers the crystals and prevents any further reaction.

Formatik - 21-12-2009 at 13:11

Quote: Originally posted by franklyn

Calcium Phosphide ( Ca3P2 ) + H2O -> ( PH3 ) Phosphine
which pyrophorically burns with a bright cherry red flame.

Departing a little from the subject, USP3944448 describes a thixotropic gel propellant using phosphides and perchloric acid dihydrate (other oxidants also).

Quote: Originally posted by woelen

When doing these demos, please be careful and only use SMALL quantities and always be prepared to cope with (too) early ignition of the mixes. All 4 of these experiments, however, are nice and spectacular demos which can be carried out safely when done carefully.

That goes without saying for all such mixtures, larger amounts become a strong dangerous fire or explosion hazard.

Quote:

I tried the NaClO3/conc. HNO3 suggestion further up in the thread, but it did not work for me. No reaction at all, the NaClO3 did not dissolve and the colorless crystals of NaClO3 became covered with a thin white crust. Apparenty some NaClO3 dissolves, giving a precipitate of NaNO3 which covers the crystals and prevents any further reaction.

Without a fuel, like sugar, I wouldn't expect any spectacular reaction here.

The most spectacular reaction I've seen was by adding a drop conc. aq. HClO4 into a drop of 90 to 99% DMSO (not vice versa so there is some excess of the latter, the acid must also be as water-free as possible attained by boiling or it won't work), a thump explosion (but no bang) and flash occurs on the liquid surface, spraying the mixture (Caution! Face shield!). Don't do more than dropwise amounts. DMF was bland, it didn't do anything except it maybe gave some fumes in the same instance. Adding a drop of acid to a few mL DMSO does the same at the surface turning the liquid deep yellow (I'm not sure what it is, don't get it on you), some ClO2 is released (ventilation needed). A good demonstration also on why oxidizers and fuels shouldn't be stored not even anywhere near each other.

Small droplets of NCl3 also detonate violently even under water from olive oil or turpentine. Although easy to make, NCl3 itself has a drawback of being extremely dangerous. Some description on violence of the reaction described in A compendium of the course of chemical instruction in the in the Medical department of the university of Pennsylvania:

"The force with which a minute portion of chloride of nitrogen explodes, on contact with oil of turpentine, would hardly be credited by those who have not witnessed this phenomenon. An open saucer of Canton china was fractured by a globule not larger than a grain of mustard seed."

[Edited on 22-12-2009 by Formatik]

franklyn - 21-12-2009 at 17:19

Quote: Originally posted by woelen

A few examples of self-ignition:

Demo 2
- Take a spatula full of powdered Na2O/NaOH mix and put this in a DRY testtube
- Add a few drops of nitromethane --> As soon as the liquid touches the solid
. a 10 cm long orange flame erupts out of the test tube!

Demo 2
Because Nitromethane is acidc , in contact with an Alkali base it will form
the anhydrous Aci-Nitromethanoate salt, a sensitive explosive.
To make Nitronate salts from Nitromethane, non-aqueous solvent such as
absolute alcohol is needed to buffer the reaction from the heat of reaction.
Which is why it instantly conflagrates if only the reactants are present.

From Bretherick's
H2C=N(O)ONa , Sodium nitromethanoate is relatively stable when solvated.
The dry salt is a sensitive and powerful explosive which may be detonated
by warming to 100°C, by a strong blow or contact with traces of water.
The potassium salt is even more sensitive.

Quote:

Demo 4
- Touch the mix with a long wet stick --> A very bright white flash occurs
. and droplets of molten silver are sprayed around[

Demo 4

. . then someone can hang you up on the Christmas Tree.

woelen - 22-12-2009 at 00:30

Quote:

The most spectacular reaction I've seen was by adding a drop conc. aq. HClO4 into a drop of 90 to 99% DMSO (not vice versa so there is some excess of the latter, the acid must also be as water-free as possible attained by boiling or it won't work)

I have 200 ml moderately concentrated HClO4 (50% by weight or so). Could this be safely concentrated to the 72% azeotrope by boiling away some water? I never had the guts to do this, because I have read and heard of explosions while the acid is concentrated and very hot. How safe is it to do this? I would love to have some HClO4 of high concentration, because so many interesting experiments can be done with that (such as the DMSO experiment, but also making NOClO4 and IO2ClO4 from NO/NO2 resp. I2O5).

[Edited on 22-12-09 by woelen]

concentration

Formatik - 22-12-2009 at 01:57

Quote: Originally posted by woelen

Aq. HClO4 is safe to heat as long as you take right precautions, like don't let any organic contaminants fall in, don't overheat it with too strong of a heat source. Just heat it over a hotplate using merely sufficient heat until you see thick white fumes (Never allow these fumes to absorb onto paper, cardboard, wood,etc. Don't even heat it near wood in case of a spill. Never heat the acid in a fume hood that it wasn't specifically designed for!), then heat after that some more, and see for yourself how much heat is needed. Do it under very good ventilation since the fumes are toxic and can have a choking effect. If done esp. in a beaker, the amount of fumes might seem massive and even after heat is removed it is also an interesting phenomenon (beats dry ice and food coloring). Try concentration with a small amount like 10mL and then see where you go from there - but beware of spitting with such amounts - it may be good to use a clamp.

[Edited on 22-12-2009 by Formatik]

The WiZard is In - 8-4-2010 at 10:19

Quote: Originally posted by Formatik

Quote:

Originally posted by PHILOU Zrealone

Hi Louis. The glycerin reaction is classical. I think KMnO4 might also ignite some glycol ethers. As a control to the 90%, in the same instance with 35% H2O2 and H2SO4 there was no reaction with acetone, not even gas evolution. But that is also at small amounts.

Dr. Ellern in his first book (bet you didn't know there are two!)
Modern Pyrotechnics, 1961. Notes that potassium permanganate
will react not only with glycerin, but also with:

ethylene glycol
erythritol
mannitol
methyglycol
monochlorohydrine
triethanolamine
acetaldehyde
benzaldehyde

Original reference:
H. Rathsburg and H Gawlick. Chem Ztg., 65, 426-7, (1941).

-----------------------------
Organic Chemistry: The practice of transmuting
vile substances into publications.
Anon.